Method for producing alkyl-indium compounds and the use thereof

Patent metadata

Field	Value
Publication number	US-9540401-B2
Application number	US-201414913026-A
Country	US
Kind code	B2
Filing date	Aug 18, 2014
Priority date	Aug 22, 2013
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

The invention relates to a method for the cost-effective and environmentally friendly production of dialkyl indium chloride in high yield and with high selectivity and purity. The dialkyl indium chloride produced according to the invention is particularly suitable, also as a result of the high purity and yield, for the production, on demand, of indium-containing precursors in high yield and with high selectivity and purity. As a result of the high purity, the indium-containing precursors that can be produced are particularly suitable for metal organic chemical vapor deposition (MOCVD) or metal organic vapor phase epitaxy (MOVPE). The novel method according to the invention is characterized by the improved execution of the method, in particular a rapid process control. Owing to targeted and extensive use of raw materials that are cost-effective and have a low environmental impact, the method is also suitable for use on an industrial scale.

First claim

The invention claimed is:

1. Process for preparing a compound (A) of the general formula:
R 2 InCl
comprising the reaction steps of
a1) reacting an indium donor with an alkyl donor to form the compound (A), the alkyl donor being alkylaluminium sesquichloride (R 3 Al 2 Cl 3 ), and the indium donor being indium trichloride (InCl 3 ),
a2) and optionally isolating compound (A) from the reaction mixture;
where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched.

2. Process according to claim 1 , where R is methyl or ethyl.

3. Process according to claim 1 , wherein an auxiliary base is also added in reaction step a1), the auxiliary base comprising at least one halide of a metal of groups 1, 2 or 13 (IA, IIA or IIIA) of the Periodic Table.

4. Process according to claim 3 , wherein the auxiliary base comprises sodium chloride, potassium chloride, aluminium chloride or mixtures thereof.

5. Process according to claim 3 , wherein the auxiliary base is a mixture of sodium chloride and potassium chloride, and wherein the molar ratio of sodium chloride to potassium chloride is between 6:3 and 8:3.

6. Process according to claim 3 , wherein the auxiliary base is a mixture of aluminium chloride, sodium chloride and potassium chloride, and wherein the molar ratio of aluminium chloride to sodium chloride to potassium chloride is 45 to 55:30 to 40:10 to 20.

7. Process according to claim 3 , wherein 0.8 to 2.5 equivalents of auxiliary base are used per equivalent of indium donor in reaction step a1).

8. Process according to claim 1 , wherein between 0.6 and 2 equivalents of alkyl donor are used per equivalent of indium donor in reaction step a1).

9. Process according to claim 1 , wherein the process comprises the isolation of compound (A) as step a2), and wherein the isolation comprises the separation of volatile constituents from the reaction mixture present in the reaction vessel and the sublimation of compound (A) from the reaction mixture.

10. Process for preparing trialkylindium of the formula R 3 In, comprising the following reaction steps:
preparing dialkylindium chloride, compound (A), of the formula R 2 InCl;
b1) reacting compound (A) with an alkyllithium to form lithium tetraalkylindate (LiInR 4 ), and isolating LiInR 4 from the reaction mixture, and
b2) reacting LiInR 4 with an indium chloride component to obtain a compound (B) of the general formula:
R 3 In

where R is as defined in claim 1 .

11. Process according to claim 10 , wherein the indium chloride component has the general formula:
R a In b Cl c
where a is a number selected from 0, 1, 2 and 3 and b is a number selected from 1 and 2 and c is a number selected from 1, 2 and 3, and where a+b+c=4 or is a multiple of 4, and where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched.

12. Process according to claim 10 , wherein the indium chloride component is selected from R 2 InCl, R 3 In 2 Cl 3 , RInCl 2 and InCl 3 .

13. Process according to claim 1 , comprising the following additional reaction steps:
c) reacting compound (A) with an alkylating agent to form compound (C) having the general formula:
R 2 InR′

where R′ is a nucleophilic radical selected from the group consisting of branched, unbranched, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched.

14. Process according to claim 13 , wherein the alkylating agent is selected from R′MgX, R′Li and R′ 3 Al.

15. Process according to claim 13 , where R is methyl, and where R′ is an Me 2 N—(CH 2 ) 3 — radical.

16. A process for preparing compound (B), comprising:
reacting compound (A having the general formula: R 2 InCl, where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched, with an alkyllithium to form lithium tetraalkylindate (LiInR 4 ),
isolating LiInR 4 from the reaction mixture, and
reacting LiInR 4 with an indium chloride component to obtain the compound (B) having the general formula: R 3 In, where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched.

17. A process for preparing compound (C), comprising:
reacting compound (A) having the general formula: R 2 InCl, where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched, with an alkylating agent to form the compound (C) having the general formula: R 2 InR′, where R′ is a nucleophilic radical selected from the group consisting of branched, unbranched, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and where R is an alkyl radical having 1 to 4 carbon atoms, and where R is branched or unbranched.

18. In a metal-organic chemical vapour deposition (MOCVD) or metal-organic vapour phase epitaxy (MOVPE), wherein the improvement comprises, utilizing a precursor of the compound (B) prepared by a process according to claim 10 .

19. In a metal-organic chemical vapour deposition (MOCVD) or metal-organic vapour phase epitaxy (MOVPE), wherein the improvement comprises, utilizing the compound (C) prepared by a process according to claim 13 .

20. Process according to claim 2 , wherein an auxiliary base is also added in reaction step a1), the auxiliary base comprising at least one halide of a metal of groups 1, 2 or 13 (IA, IIA or IIIA) of the Periodic Table.

Assignees

• Umicore Ag & Co Kg

Inventors

• Sundermeyer Joerg
• Frey Annika
• Schorn Wolf
• Grosse-Hagenbrock David
• Karch Ralf
• Rivas-Nass Andreas
• Woerner Eileen
• Doppiu Angelino

Classifications

• H10F71/00

  Manufacture or treatment of devices covered by this subclass (patterning processes to connect thin photovoltaic cells in integrated devices, or assemblies of multiple devices, having photovoltaic cells H10F19/33; manufacture or treatment of encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells H10F19/80; manufacture or treatment of integrated devices, or assemblies of multiple devices, comprising at least one element in which radiation controls the flow of current H10F39/00) · CPC title

• H10H20/01

  Manufacture or treatment · CPC title

• C07F5/00 Primary

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title